Reflective article and method for the preparation thereof

ABSTRACT

A reflective article useful, for example, in automotive headlights includes a haze-prevention layer between a heat-resistant thermoplastic substrate and a reflective metal layer. The haze-prevention layer includes a metal having a tensile modulus of at least about 15×10 6  pounds per square inch. The article resists hazing of the reflective layer at elevated temperatures.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional ApplicationSerial No. 60/405,389, filed Aug. 23, 2002.

BACKGROUND OF THE INVENTION

[0002] Reflective articles comprising a thermoplastic substrate and areflective metal layer are currently employed in a variety of productapplications, including automotive headlight reflectors. Such articlesmay perform well at ambient temperatures, but at the elevatedtemperatures encountered in certain manufacturing and use conditions,their reflectivity may be impaired by the formation of haze in thereflective coating.

[0003] There is therefore a need for reflective articles that maintaintheir reflectivity at elevated temperatures.

BRIEF DESCRIPTION OF THE INVENTION

[0004] One embodiment is a reflective article exhibiting improvedheat-resistance, comprising: a substrate comprising an amorphousthermoplastic resin having a heat distortion temperature of at leastabout 140° C. measured at 66 pounds per square inch (psi) according toASTM D648; a reflective metal layer; and a haze-prevention layerinterposed between the substrate and the reflective metal layer, whereinthe haze-prevention layer comprises a metal having a tensile modulus ofat least about 15×10⁶ pounds per square inch measured at 25° C.according to ASTM D638.

[0005] Other embodiments, including a method of preparing the reflectivearticle, are described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006]FIG. 1 is an exploded view of a reflective article 10 comprising athermoplastic substrate 20, a reflective metal layer 30, and ahaze-prevention layer 40.

DETAILED DESCRIPTION OF THE INVENTION

[0007] One embodiment is a reflective article, comprising: a substratecomprising an amorphous thermoplastic resin having a heat distortiontemperature of at least about 140° C. measured at 66 psi according toASTM D648; a reflective metal layer; and a haze-prevention layerinterposed between the substrate and the reflective metal layer, whereinthe haze-prevention layer comprises a metal having a tensile modulus ofat least about 15×10⁶ pounds per square inch measured at 25° C.according to ASTM D638.

[0008] During the commercial development of reflectors for automotiveheadlights, it was sometimes observed that reflectors prepared by directmetalization of a thermoplastic substrate would initially exhibitexcellent reflectivity, but under conditions of use, hazing of thereflective surface would occur, leading to failure of the part. Throughextensive research on a variety of materials, the present inventors havediscovered that haze-formation under high-temperature conditions can bereduced or eliminated by interposing between the thermoplastic substrateand the reflective metal layer a haze-prevention layer having a tensilemodulus of at least about 15×10⁶ pounds per square inch measured at 25°C. according to ASTM D638. As described in detail below, a variety ofmaterials are suitable for fabricating the haze-prevention layer, butthey are united in their mechanical characteristics.

[0009] The substrate comprises an amorphous thermoplastic resin having aheat distortion temperature of at least about 140° C., preferably atleast about 170° C., more preferably at least about 185° C., still morepreferably at least about 200° C., measured at 66 psi according to ASTMD648. Suitable thermoplastic resins include, for example,polyetherimides, polyetherimide sulfones, polysulfones,polyethersulfones, polyphenylene ether sulfones, poly(arylene ether)s,polycarbonates, polyester carbonates, polyarylates, and the like, andmixtures thereof. These thermoplastics and methods for their preparationare known in the art.

[0010] Preferred polyetherimides include those comprising structuralunits of the formula (I)

[0011] wherein the divalent T moiety bridges the 3,3′, 3,4′, 4,3′, or4,4′ positions of the aryl rings of the respective aryl imide moietiesof formula (I); T is —O— or a group of the formula —O-Z-O—; Z is adivalent radical selected from the group consisting of formulae (II)

[0012] wherein X is a member selected from the group consisting ofdivalent radicals of the formulae (III)

[0013] wherein y is an integer of 1 to about 5, and q is 0 or 1; R is adivalent organic radical selected from (a) aromatic hydrocarbon radicalshaving 6 to about 20 carbon atoms and halogenated derivatives thereof,(b) alkylene radicals having 2 to about 20 carbon atoms, (c)cycloalkylene radicals having 3 to about 20 carbon atoms, and (d)divalent radicals of the general formula (IV)

[0014] where Q is a covalent bond or a member selected from the groupconsisting of formulae (V)

[0015] where y′ is an integer from 1 to about 5.

[0016] In the formulas above, when X or Q comprises a divalent sulfonelinkage, the polyetherimide may be considered a polyetherimide sulfone.

[0017] Generally, useful polyetherimides have a melt index of about 0.1to about 10 grams per minute (g/min), as measured by American Societyfor Testing Materials (ASTM) D1238 at 337° C., using a 6.6 kilogramweight.

[0018] In a preferred embodiment, the polyetherimide resin has a weightaverage molecular weight of about 10,000 to about 150,000 atomic massunits (AMU), as measured by gel permeation chromatography usingpolystyrene standards. Such polyetherimide resins typically have anintrinsic viscosity greater than about 0.2 deciliters per gram measuredin m-cresol at 25° C. An intrinsic viscosity of at least about 0.35deciliters per gram may be preferred. Also, an intrinsic viscosity of upto about 0.7 deciliters per gram may be preferred.

[0019] Included among the many methods of making the polyetherimideresin are those described, for example, in U.S. Pat. Nos. 3,847,867 toHeath et al., 3,850,885 to Takekoshi et al., 3,852,242 and 3,855,178 toWhite, and 3,983,093 to Williams et al.

[0020] In a preferred embodiment, the polyetherimide resin comprisesstructural units according to formula (I) wherein each R isindependently paraphenylene or metaphenylene and T is a divalent radicalof the formula (VI).

[0021] A particularly preferred polyetherimide resin is the reactionproduct formed by melt polymerization of2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride with one ormore of paraphenylene diamine and metaphenylene diamine. Thepolyetherimides are commercially available from General Electric Companyas ULTEM® resins, including, for example, ULTEM® 1000, ULTEM® 1010,ULTEM® 6000, ULTEM® XH6050, and ULTEM®G CRS5000. Additional descriptionof polyetherimide polymers may be found, for example, in ASTM 5205,Standard Classification System for Polyetherimide (PEI) Materials.

[0022] Polysulfones suitable for use in the thermoplastic substrate arepolymeric comprising repeating units having at least one sulfone group.Polysulfones and methods for their preparation are well known in the artand described, for example, in U.S. Pat. No. 3,642,946 to Grabowski etal.; and Kirk-Othmer, Encyclopedia of Chemical Technology, SecondEdition, Vol. 16, pp. 272- 281 (1968). Representative polymers of thistype include polysulfones, polyether sulfones, and polyphenyl sulfones.

[0023] The polysulfones that may be utilized in the instant inventioncontain at least one recurring structural unit represented by thegeneral formula (VU)

[0024] wherein each occurrence of Ar is independently unsubstitutedphenylene or phenylene substituted with phenyl, C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, halogen, nitro, or the like; and each occurrence of A isindependently a direct carbon-to-carbon bond, C₁-C₁₂ alkylidene, C₃-C₈cycloalkylidene, carbonyl sulfoxide, sulfur, sulfone, azo, imino,oxygen, or the like.

[0025] The polysulfones of Formula (VII) are preferably derived fromdichlorodiphenyl sulfones reacted with bisphenols. A second group ofsulfones represented by Formula I is one in which each Ar is phenyleneand A is sulfone. A third major group of polysulfones represented byFormula I are those wherein each. Ar is phenylene and A is oxygen, i.e.,the polyarylethersulfones. When Ar is phenylene, it should preferably beeither meta or para and may be substituted in the ring positions withC₁-C₆ alkyl groups, C₁-C₆ alkoxy groups, or the like. Particularlyuseful polysulfones are those derived from disulfonyl chlorides such as4,4-biphenyldisulfonyl chloride reacted with 4,4′-dihydroxydiphenylether.

[0026] The polyarylethersulfones, including polyphenylene ethersulfones, contain at least the following recurring structural units

[0027] wherein R, R¹ and R² are independently selected from C₁-C₆ alkyl,C₄-C₈ cycloalkyl, and halogen radicals; W is a C₂-C₈ alkylene, a C₁-C₈alkylidene, a cycloalkylene or cycloalkylidene radical containing from 4to about 16 ring carbon atoms, or the like; b is 0 or 1; and n, n1, andn2 are independently 0, 1, 2, 3, or 4. Additional description ofpolysulfone may be found, for example, in ASTM D6394, StandardSpecification for Sulfone Plastics (SP).

[0028] Suitable poly(arylene ether)s include polyphenylene ether (PPE)and poly(arylene ether) copolymers; graft copolymers; poly(aryleneether) ether ionomers; and block copolymers of alkenyl aromaticcompounds, vinyl aromatic compounds, and poly(arylene ether), and thelike; and combinations comprising at least one of the foregoing; and thelike. Poly(arylene ether)s are known polymers comprising a plurality ofstructural units of the formula

[0029] wherein for each structural unit, each Q¹ is independentlyhalogen, primary or secondary C₁-C₈ alkyl, phenyl, C₁-C₈ haloalkyl,C₁-C₈ aminoalkyl, C₁-C₈ hydrocarbonoxy, or C₂-C₈ halohydrocarbonoxywherein at least two carbon atoms separate the halogen and oxygen atoms;and each Q² is independently hydrogen, halogen, primary or secondaryC₁-C₈ alkyl, phenyl, C₁-C₈ haloalkyl, C₁-C₈ aminoalkyl, C₁-C₈hydrocarbonoxy, or C₂-C₈ halohydrocarbonoxy wherein at least two carbonatoms separate the halogen and oxygen atoms. Preferably, each Q, isalkyl or phenyl, especially C₁-C₄ alkyl, and each Q² is independentlyhydrogen or methyl.

[0030] Both homopolymer and copolymer poly(arylene ether)s are included.The preferred homopolymers are those comprising 2,6-dimethylphenyleneether units. Suitable copolymers include random copolymers comprising,for example, such units in combination with2,3,6-trimethyl-1,4-phenylene ether units or copolymers derived fromcopolymerization of 2,6-dimethylphenol with 2,3,6-trimethylphenol. Suchcopolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, especiallythose containing about 5 to about 50 weight percent of units derivedfrom 2,3,6-trimethylphenol, are particularly preferred for their heatresistance. Also included are poly(arylene ether)s containing moietiesprepared by grafting vinyl monomers or polymers such as polystyrenes, aswell as coupled poly(arylene ether) in which coupling agents such as lowmolecular weight polycarbonates, quinones, heterocycles and formalsundergo reaction in known manner with the hydroxy groups of twopoly(arylene ether) chains to produce a higher molecular weight polymer.Poly(arylene ether)s of the present invention further includecombinations of any of the above.

[0031] The poly(arylene ether) generally has a number average molecularweight of about 3,000 to about 40,000 atomic mass units (AMU) and aweight average molecular weight of about 20,000 to about 80,000 AMU, asdetermined by gel permeation chromatography. The poly(arylene ether)generally may have an intrinsic viscosity of about 0.2 to about 0.6deciliters per gram (dL/g) as measured in chloroform at 25° C. Withinthis range, the intrinsic viscosity may preferably be up to about 0.5dL/g, more preferably up to about 0.47 dL/g. Also within this range, theintrinsic viscosity may preferably be at least about 0.3 dL/g. It isalso possible to utilize a high intrinsic viscosity poly(arylene ether)and a low intrinsic viscosity poly(arylene ether) in combination.Determining an exact ratio, when two intrinsic viscosities are used,will depend on the exact intrinsic viscosities of the poly(aryleneether)s used and the ultimate physical properties desired.

[0032] The poly(arylene ether)s are typically prepared by the oxidativecoupling of at least one monohydroxyaromatic compound such as2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are generallyemployed for such coupling. They typically contain at least one heavymetal compound such as a copper, manganese or cobalt compound, usuallyin combination with various other materials. Suitable methods forpreparing poly(arylene ether)s are described, for example, in U.S. Pat.Nos. 3,306,874 and 3,306,875 to Hay, and 4,011,200 and 4,038,343 toYonemitsu et al.

[0033] Suitable polycarbonates may be prepared by reacting a dihydricphenol with a carbonate precursor, such as phosgene, a haloformate, or acarbonate ester. Generally, such carbonate polymers possess recurringstructural units of the formula

[0034] wherein A is a divalent aromatic radical of the dihydric phenolemployed in the polymer producing reaction. Preferably, the carbonatepolymers used to provide the resinous mixtures of the invention have anintrinsic viscosity (as measured in methylene chloride at 25° C.) ofabout 0.30 to about 1.00 dL/g. The dihydric phenols employed to providesuch aromatic carbonate polymers may be mononuclear or polynucleararomatic compounds, containing as functional groups two hydroxyradicals, each of which is attached directly to a carbon atom of anaromatic nucleus. Typical dihydric phenols include, for example,2,2-bis(4-hydroxyphenyl)propane (bisphenol A); hydroquinone; resorcinol;2,2-bis(4-hydroxyphenyl)pentane; 2,4′-(dihydroxydiphenyl)methane;bis(2-hydroxyphenyl)methane; bis(4-hydroxyphenyl)methane;bis(4-hydroxy-5-nitrophenyl)methane; 1,1 -bis(4-hydroxyphenyl)ethane;3,3-bis(4-hydroxyphenyl)pentane; 2,2-dihydroxydiphenyl;2,6-dihydroxynaphthalene; bis(4-hydroxydiphenyl)sulfone;bis(3,5-diethyl-4-hydroxyphenyl)sulfone;2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; 2,4′-dihydroxydiphenylsulfone; 5′-chloro-2,4′-dihydroxydiphenyl sulfone;bis(4-hydroxyphenyl)diphenyl sulfone; 4,4′-dihydroxydiphenyl ether;4,4′-dihydroxy-3,3′-dichlorodiphenyl ether;4,4-dihydroxy-2,5-dihydroxydiphenyl ether; and the like.

[0035] Other dihydric phenols suitable for use in the preparation ofpolycarbonate resins are described, for example, in U.S. Pat. Nos.2,999,835 to Goldberg, 3,334,154 to Kim, and 4,131,575 to Adelmann etal.

[0036] These aromatic polycarbonates can be manufactured by knownprocesses, such as, for example and as mentioned above, by reacting adihydric phenol with a carbonate precursor, such as phosgene, inaccordance with methods set forth in the above-cited literature and inU.S. Pat. No. 4,123,436 to Holub et al., or by transesterificationprocesses such as are disclosed in U.S. Pat. No. 3,153,008 to Fox, aswell as other processes known to those skilled in the art.

[0037] It is also possible to employ two or more different dihydricphenols or a copolymer of a dihydric phenol with a glycol or with ahydroxy- or acid-terminated polyester or with a dibasic acid in theevent a carbonate copolymer or interpolymer rather than a homopolymer isdesired. Branched polycarbonates are also useful, such as are describedin U.S. Pat. No. 4,001,184 to Scott. Also, there can be utilized blendsof linear polycarbonate and a branched polycarbonate. Moreover, blendsof any of the above materials may be employed in the practice of thisinvention to provide the aromatic polycarbonate.

[0038] These polycarbonates may be branched or linear and generally willhave a weight average molecular weight of about 10,000 to about 200,000AMU, preferably from about 20,000 to about 100,000 as measured by gelpermeation chromatography. The polycarbonates of the invention canemploy a variety of end groups to improve performance. Bulkymonophenols, such as cumyl phenol, are preferred.

[0039] Suitable polycarbonates further include those derived frombisphenols containing alkyl cyclohexane units. Such polycarbonates havestructural units corresponding to the structure

[0040] wherein R^(a)-R^(d) are each independently hydrogen, C₁-C₁₂hydrocarbyl, or halogen; and R^(e)-R^(i) are each independentlyhydrogen, C₁-C₁₂ hydrocarbyl. As used herein, “hydrocarbyl” refers to aresidue that contains only carbon and hydrogen. The residue may bealiphatic or aromatic, straight-chain, cyclic, bicyclic, branched,saturated, or unsaturated. The hydrocarbyl residue, when so statedhowever, may contain heteroatoms over and above the carbon and hydrogenmembers of the substituent residue. Thus, when specifically noted ascontaining such heteroatoms, the hydrocarbyl residue may also containcarbonyl groups, amino groups, hydroxyl groups, or the like, or it maycontain heteroatoms within the backbone of the hydrocarbyl residue.Alkyl cyclohexane containing bisphenols, for example the reactionproduct of two moles of a phenol with one mole of a hydrogenatedisophorone, are useful for making polycarbonate resins with high glasstransition temperatures and high heat distortion temperatures. Suchisophorone bisphenol-containing polycarbonates have structural unitscorresponding to the structure

[0041] wherein R^(a)-R^(d) are as defined above. These isophoronebisphenol based resins, including polycarbonate copolymers madecontaining non-alkyl cyclohexane bisphenols and blends of alkylcyclohexyl bisphenol containing polycarbonates with non-alkyl cyclohexylbisphenol polycarbonates, are supplied by Bayer Co. under the APEC tradename and described, for example, in U.S. Pat. No. 5,034,458 to Serini etal.

[0042] Suitable thermoplastic resins further include “polyarylates,”which is the common term referring to polyesters of aromaticdicarboxylic acids and bisphenols. Polyarylate copolymers includingcarbonate linkages in addition to the aryl ester linkages, known aspolyester-carbonates, are also suitable. These resins may be used aloneor in combination with each other or more preferably in combination withbisphenol polycarbonates. These resins can be prepared in solution or bymelt polymerization from aromatic dicarboxylic acids or their esterforming derivatives and bisphenols and their derivatives. Suitabledicarboxylic acids are iso- and terephthalic acid, their esters or acidchlorides. A preferred bisphenol is bisphenol A or its diacetatederivative. Polyester carbonates and polyarylates may also containlinkages derived from hydroxy carboxylic acids such as hydroxy benzoicacid. The most preferred polyester-carbonates and polyarylates areamorphous resins derived from bisphenol A and mixtures of isophthalicand terephthalic acid. Suitable polyarylates and their preparation aredescribed, for example, in U.S. Pat. No. 4,663,421 to Mark. Suitablepolyester-carbonates and their preparation are described, for example,in U.S. Pat. Nos. 3,169,121 to Goldberg, and 4,156,069 to Prevorsek etal.

[0043] In one embodiment, the substrate comprises at least about 50% byweight, preferably at least about 80% by weight, more preferably atleast about 90% by weight, still more preferably at least about 95% byweight, of the thermoplastic resin.

[0044] In one embodiment the substrate comprises, in addition to thethermoplastic resin, an inorganic filler such as, for example, talc,mica, clay, titanium dioxide, zinc oxide, zinc sulfide, wollastonite, orthe like, or a mixture thereof.

[0045] In another embodiment, the substrate is substantially free ofinorganic filler. “Substantially free of inorganic filler” is definedherein as comprising less than 0.1 weight percent of inorganic filler.It may be preferred that the substrate comprises less than 0.01 weightpercent of inorganic filler.

[0046] The substrate resin may further contain additives to improve meltprocessing, molding or part stability. Useful additives includelubricants and mold release agents, such as aliphatic esters, forexample pentaerythritol tetrastearate, or polyolefins, for example highdensity polyethylene. Stabilizers, such as aryl phosphite and hinderedphenols may also be blended with the substrate resin. Other additivesinclude compounds to reduce static charge build up. If employed in thesubstrate, it is important to select such additives so that they arethermally stable, show low volatility and do not contribute to hazing inthe metallized article.

[0047] In one embodiment, the amorphous thermoplastic also has a densityless than 1.7 grams/milliliter (g/mL), preferably less than 1.6 g/mL,more preferably less than 1.5 g/mL. The density of the amorphousthermoplastic resin may be determined at 25° C. according to ASTM D792.The amorphous thermoplastic resin is thus less dense than bulk moldingcompounds that have often been used to form reflective articles. Whenthe reflective article is a headlight reflector, the use of theamorphous resin reduces the weight of the headlight thereby contributesto weight reductions that allow more vehicle miles per gallon of fuel.

[0048] In one embodiment, the amorphous thermoplastic has an organicvolatiles content less than 1,000 parts per million by weight,preferably less than 750 parts per million by weight, more preferablyless than 500 parts per million by weight, measured according to ASTMD4526. As specified in ASTM D4526, the volatiles are determined bysampling a headspace in equilibrium with the thermoplastic at 90° C.,and they are quantified using flame ionization detection. In thisembodiment, the organic volatiles content is thus lower than that ofbulk molding compounds, which may contain high concentrations ofresidual monomers that outgas at elevated temperatures and decrease thereflectivity of the reflective metal layer.

[0049] The dimensions of the substrate will be dictated by the use ofthe reflective article. For example, when the reflective article is aheadlight reflector, it may have a thickness of about 0.1 to about 20millimeters in the dimension perpendicular to the haze-prevention layerand the reflective metal layer; within this range, the thickness maypreferably be at least about 0.5 millimeters, more preferably at leastabout 1 millimeter; also within this range, the thickness may preferablybe up to about 10 millimeters, more preferably up to about 8millimeters.

[0050] The reflective article comprises a reflective metal layer. Metalssuitable for use in the reflective metal layer include the metals ofGroups IIIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, and IIB of the periodictable. Mixtures and alloys of these metals may also be used. Preferredmetals include aluminum, silver, gold, nickel, palladium, platinum,copper, and the like, and alloys comprising at least one of theforegoing metals. Aluminum and its alloys are particularly preferredmetals for the reflective metal layer.

[0051] The reflective metal layer may be formed using methods known inthe art, including sputtering, vacuum metal deposition, vapor arcdeposition, plasma chemical vapor deposition, thermal vapor metaldeposition, and ion plating.

[0052] The reflective metal layer may have a thickness of about 1 toabout 1000 nanometers. Within this range, the thickness may preferablybe at least about 10 nanometers, more preferably at least about 20nanometers. Also within this range, the thickness may preferably be upto about 500 nanometers, more preferably up to about 200 nanometers.

[0053] The reflective article comprises a haze-prevention layerinterposed between the substrate and the reflective metal layer. Thehaze-prevention layer comprises a metal having a tensile modulus of atleast about 15×10⁶ pounds per square inch, preferably at least about20×10⁶ pounds per square inch, more preferably at least about 30×10⁶pounds per square inch, measured at 25° C. according to ASTM D638.

[0054] Metals preferred for their high tensile modulus values includeantimony, bismuth, cerium, chromium, cobalt, copper, iridium, iron,molybdenum, nickel, palladium, platinum, rhodium, tantalum, titanium,tungsten, vanadium, and alloys thereof. Particularly preferred metalsfor use in the haze-prevention layer include chromium and its alloys.

[0055] The haze-prevention layer may be formed using known metal coatingmethods, including, for example, sputtering, vacuum metal deposition,vapor arc deposition, plasma chemical vapor deposition, thermal vapormetal deposition, and ion plating.

[0056] In one embodiment, the haze-prevention layer comprises at leastabout 50 weight percent, preferably at least about 80 weight percent,more preferably at least about 90 weight percent, still more preferablyat least about 95 weight percent of the high tensile modulus metal,based on the total weight of the haze-prevention layer.

[0057] The thickness of the haze-prevention layer will depend on itscomposition, but it is generally about 1 to about 1000 nanometers.Within this range, the thickness may preferably be at least about 20nanometers, more preferably at least about 50 nanometers. Also withinthis range, the thickness may preferably be up to about 500 nanometers,more preferably up to about 200 nanometers.

[0058] Although the substrate is well suited for direct application of ahaze-prevention layer, it is also possible to pre-coat the substratewith a primer before applying the haze-prevention layer. It may also beadvantageous to further coat the reflective article with a clear, hardprotective layer to protect the reflective metal layer from scratching,oxidation, or related problems. The protective layer may, preferably,exhibit a percent transmittance greater than 90 percent measurednanometers according to ASTM D1003. The protective layer may,preferably, exhibit a yellowness index less than 5 measured according toASTM D1925. Suitable compositions and methods for preparing protectivemetal oxide layers are described, for example, in U.S. Pat. Nos.6,110,544 to Yang et al., and 6,379,757 B1 to lacovangelo. Thus, in oneembodiment, the reflective article includes a protective layer, whereinthe haze-prevention layer is interposed between substrate and thereflective layer, and the reflective layer is interposed between thehaze-prevention layer and the protective layer.

[0059] In a preferred embodiment, the reflective article comprises asurface having a reflectivity of at least 80%, more preferably at leastabout 85%, even more preferably at least about 90%, measured accordingto ASTM D523. In a highly preferred embodiment, the reflective articlecomprises a surface having a reflectivity of at least 80%, morepreferably at least about 85%, even more preferably at least about 90%,after 15 minutes exposure to a temperature corresponding to the lowestheat distortion temperature of any thermoplastic resin in the substrate.The temperature at which a reflective article will resist hazing will beinfluenced by the nature of the thermoplastic substrate. With resinshaving a higher heat distortion temperature or glass transitiontemperature giving higher heat resistance. For a given resin substrate,use of a high modulus metal haze reducing layer, placed on the substrateand covered with second reflective metal layer, will provide greaterresistance to haze formation than the use of a reflective layer alone.

[0060] It will be understood that the haze-prevention layer and thereflective metal layer are distinct, and that it is not intended for asingle metal layer to perform both functions. In one embodiment, thehaze-prevention layer and the reflective layer have differentcompositions.

[0061]FIG. 1 presents an exploded perspective view of a section of areflective article 10. Haze-prevention layer 40 is interposed betweensubstrate 20 and reflective metal layer 30.

[0062] The reflective article may be used, for example, as an automotiveheadlight reflector, a reflector incorporated into a projector lamp, amirror of any shape and curvature.. Headlight reflectors and theirpreparation is described, for example, in U.S. Pat. Nos. 5,503,934 toMaas et al. and 6,355,723 B1 to van Baal et al.

[0063] In an embodiment preferred for its simplicity, the reflectivearticle consists essentially of: a substrate comprising an amorphousthermoplastic resin having a heat distortion temperature of at leastabout 140° C. measured at 66 psi according to ASTM D648; a reflectivemetal layer; and a haze-prevention layer interposed between thesubstrate and the reflective metal layer, wherein the haze-preventionlayer comprises a metal having a tensile modulus of at least about15×10⁶ pounds per square inch measured at 25° C. according to ASTM D638.

[0064] In a preferred embodiment, the reflective article comprises: asubstrate comprising a polysulfone resin having a glass transitiontemperature of at least about 170° C.; a reflective metal layercomprising aluminum; and a haze-prevention layer interposed between thesubstrate and the reflective metal layer, wherein the haze-preventionlayer comprises chromium and has a tensile modulus of at least about30×10⁶ pounds per square inch measured at 25° C. according to ASTM D638.

[0065] Another embodiment is a method for preparing a reflectivearticle, comprising: applying a haze-prevention layer to a surface of asubstrate, wherein the haze-prevention layer comprises a metal having atensile modulus of at least about 15×10⁶ pounds per square inch measuredat 25° C. according to ASTM D638, and wherein the substrate comprises anamorphous thermoplastic resin having a heat distortion temperature of atleast about 140° C. measured at 66 psi according to ASTM D648; andapplying a reflective metal layer to a surface of the haze-preventionlayer.

[0066] The invention is further illustrated by the followingnon-limiting examples.

COMPARATIVE EXAMPLE 1

[0067] A 3.2 millimeter thick plaque of polyetherimide (ULTEM® 1010) wasmetallized by sputtering under vacuum with aluminum using a DC magnetronsource set at 300 watts to form a reflective layer having a thickness ofabout 100-200 nanometers. The plaque was placed in a convection air ovenset sequentially at 190, 200, and215° C. After 15 minutes at 215° C.,the reflective layer appeared hazy and blushed.

COMPARATIVE EXAMPLE 2

[0068] The procedure of Comparative Example 1 was followed, except thatthe polyetherimide plaque was coated by DC magnetron sputtering with a60 nanometer thickness of gold prior to coating with a 100-200 nanometerthick layer of aluminum. Oven treatment of this sample produced resultssimilar to those of the sample without gold: after 15 minutes at 215°C., the reflective layer appeared hazy and blushed.

COMPARATIVE EXAMPLE 3

[0069] The procedure of Comparative Example 1 was followed, except thatthe polyetherimide plaque coated by DC magnetron sputtering with a 60nanometer layer of gold was not metallized with aluminum. Oven treatmentof this sample produced results similar to those of the sample withaluminum: after 15 minutes at 215° C., the reflective layer appearedhazy and blushed.

EXAMPLE 1

[0070] A 3.2 mm thick plaque of polyetherimide (ULTEM® 1010) wasmetallized by sputtering under vacuum with chromium using a DC magnetronsource set at 300 watts to form a 15 nanometer chromium haze-reductionlayer, which was subsequently coated with a 100-200 nanometer aluminumreflective layer. Haze was observed on the reflective layer after 30minutes at 215° C. in the convection oven. The time to develop haze at215° C. was doubled compared to Comparative Example 1 with a no hazereduction layer or to Comparative Example 3 with a gold layer under areflective aluminum layer.

EXAMPLE 2

[0071] The procedure of Example 1 was followed, except that thethickness of the chromium haze reduction layer was increased to 100nanometers. Haze was observed on the reflective layer after 75 minutesat 215° C. in the convection oven Comparing Example 1 to Example 2 showsthat time to haze increases as a function of increasing chromiumhaze-prevention layer thickness.

[0072] While the invention has been described with reference to apreferred embodiment, it will be understood by those skilled in the artthat various changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

[0073] All cited patents, patent applications, and other references areincorporated herein by reference in their entirety.

1. A reflective article, comprising: a substrate comprising an amorphousthermoplastic resin having a heat distortion temperature of at leastabout 140° C. measured at 66 pounds per square inch according to ASTMD648; a reflective metal layer; and a haze-prevention layer interposedbetween the substrate and the reflective metal layer, wherein thehaze-prevention layer comprises a metal having a tensile modulus of atleast about 15×10⁶ pounds per square inch measured at 25° C. accordingto ASTM D638.
 2. The reflective article of claim 1, wherein theamorphous thermoplastic resin is selected from polyetherimides,polyetherimide sulfones, polysulfones, polyethersulfones, polyphenyleneether sulfones, poly(arylene ether)s, polycarbonates, polyestercarbonates, polyarylates, and mixtures thereof.
 3. The reflectivearticle of claim 1, wherein the amorphous thermoplastic resin comprisesa polyetherimide.
 4. The reflective article of claim 1, wherein thesubstrate is substantially free of inorganic filler.
 5. The reflectivearticle of claim 1, wherein the substrate has a thickness of about 0.1to about 20 millimeters in a dimension perpendicular to thehaze-prevention layer and the reflective metal layer.
 6. The reflectivearticle of claim 1, wherein the reflective metal layer comprises a metalselected from the group consisting of aluminum, silver, gold, nickel,palladium, platinum, copper, and alloys thereof.
 7. The reflectivearticle of claim 1, wherein the reflective metal layer comprisesaluminum.
 8. The reflective article of claim 1, wherein the reflectivemetal layer has a thickness of about 10 to about 1000 nanometers.
 9. Thereflective article of claim 1, wherein the haze-prevention layercomprises a metal selected from antimony, chromium, cobalt, copper,iridium, iron, molybdenum, nickel, palladium, platinum, rhenium,rhodium, tantalum, titanium, tungsten, vanadium, and alloys thereof. 10.The reflective article of claim 1, wherein the haze-prevention layercomprises chromium.
 11. The reflective article of claim 1, wherein thehaze-prevention layer has a thickness of about 1 to about 1000nanometers.
 12. The reflective article of claim 1, further comprising aprotective layer having a percent transmittance of at least 90% measuredaccording to ASTM D1003; wherein the reflective layer is interposedbetween the haze-prevention layer and the protective layer.
 13. Thereflective article of claim 1, comprising a surface with a reflectivityof at least 80% measured according to ASTM D523.
 14. The reflectivearticle of claim 1, wherein the article is an automotive headlightreflector.
 15. A reflective article, consisting essentially of: asubstrate comprising an amorphous thermoplastic resin having a heatdistortion temperature of at least about 140° C. measured at 66 poundsper square inch according to ASTM D648; a reflective metal layer; and ahaze-prevention layer interposed between the substrate and thereflective metal layer, wherein the haze-prevention layer comprises ametal having a tensile modulus of at least about 15×10⁶ pounds persquare inch measured at 25° C. according to ASTM D638.
 16. A reflectivearticle, comprising: a substrate comprising a polyetherimide resinhaving a glass transition temperature of at least about 170° C; areflective metal layer comprising aluminum; and a haze-prevention layerinterposed between the substrate and the reflective metal layer, whereinthe haze-prevention layer comprises chromium and has a tensile modulusof at least about 30×10⁶ pounds per square inch measured at 25° C.according to ASTM D638.
 17. The reflective article of claim 16, furthercomprising a protective layer having a percent transmittance of at least90% measured according to ASTM D1003; wherein the reflective layer isinterposed between the haze-prevention layer and the protective layer.18. A method for preparing a reflective article, comprising: applying ahaze-prevention layer to a surface of a substrate, wherein thehaze-prevention layer comprises a metal having a tensile modulus of atleast about 15×10⁶ pounds per square inch measured at 25° C. accordingto ASTM D638, and wherein the substrate comprises an amorphousthermoplastic resin having a heat distortion temperature of at leastabout 140° C. measured at 66 pounds per square inch according to ASTMD648; and applying a reflective metal layer to a surface of thehaze-prevention layer.